Enliang Wang

Momentum imaging spectrometer for molecular fragmentation dynamics induced by pulsed electron beam

A momentum imaging spectrometer has been built for studying the electron impact molecular fragmentation dynamics. The setup consists of a pulsed electron gun and a time of flight system as well as a two-dimensional time and position sensitive multi-hit detector. The charged fragments with kinetic energy up to 10 eV can be detected in 4π solid angles and their three-dimensional momentum vectors can be reconstructed. The apparatus is tested by electron impact ionization of Ar and dissociative ionization of CO2. By analyzing the ion-ion coincidence spectra, the complete and incomplete Coulomb fragmentation channels for CO2(2+) and CO2(3+) are identified. The kinetic energy release (KER) and angular correlation for the two-body breakup channel CO2(2+*) → O(+) + CO(+) are reported. The peak value of total KER is found to be 6.8 eV which is consistent with the previous photoion-photoion coincidence studies, and the correlation angle of O(+) and CO(+) is also explicitly determined to be 172.5°.

High-resolution electron momentum spectroscopy of valence satellites of carbon disulfide

The binding energy spectrum of carbon disulphide (CS(2)) in the energy range of 9-23 eV has been measured by a high-resolution (e,2e) spectrometer employing asymmetric noncoplanar kinematics at an impact energy of 2500 eV plus the binding energy. Taking the advantage of the high energy resolution of 0.54 eV, four main peaks and five satellites in the outer-valence region are resolved. The assignments and pole strengths for these satellite states are achieved by comparing the experimental electron momentum profiles with the corresponding theoretical ones calculated using Hartree-Fock and density functional theory methods. The results are also compared in detail with the recent SAC-CI general-R calculations. General agreement is satisfactory, while the present experiment suggests cooperative contributions from (2)Π(u), (2)Σ(g)(+) states to satellite 2 and (2)Σ(g)(+), (2)Π(g) states to satellite 3. Besides, relatively low pole strength for X (2)Π(g) state is obtained which contradicts all the theoretical calculations [2ph-TDA, ADC(3), SAC-CI general-R, ADC(4)] so far.

Fragmentation dynamics of carbonyl sulfide in collision with 500 eV electron

The fragmentation dynamics of OCSq+ (q = 2, 3, 4) induced by electron collision at an impact energy of 500 eV is studied. By using the momentum imaging technique, the three dimensional momentum vectors of all the fragments are obtained, which enables us to analyse both the kinetic energy release and the momentum correlations for a certain fragmentation channel. Up to fifteen dissociation channels are analyzed including six, five, and four channels for two-body, and incomplete and complete three-body Coulomb fragmentations. For three-body dissociation, the fragmentation mechanisms are investigated with the help of Dalitz plot and Newton diagram. It is found that the sequential fragmentation involves in OCS2+→O+C++S+ with S+ emitted first and in OCS3+→O++C++S+ with O-C and C-S bonds breaking first. The remaining channels, however, always dissociate through a concerted mechanism. The relative intensities of the channels are also presented in this work.

Electron Momentum Spectroscopy Investigation of Molecular Conformations of Ethanol Considering Vibrational Effects

The interpretation of experimental electron momentum distributions (EMDs) of ethanol, one of the simplest molecules having conformers, has confused researchers for years. High-level calculations of Dyson orbital EMDs by thermally averaging the gauche and trans conformers as well as molecular dynamical simulations failed to quantitatively reproduce the experiments for some of the outer valence orbitals. In this work, the valence shell electron binding energy spectrum and EMDs of ethanol are revisited by the high-sensitivity electron momentum spectrometer employing symmetric noncoplanar geometry at an incident energy of 1200 eV plus binding energy, together with a detailed analysis of the influence of vibrational motions on the EMDs for the two conformers employing a harmonic analytical quantum mechanical (HAQM) approach by taking into account all of the vibrational modes. The significant discrepancies between theories and experiments in previous works have now been interpreted quantitatively, indicating that the vibrational effect plays a significant role in reproducing the experimental results, not only through the low-frequency OH and CH3 torsion modes but also through other high-frequency ones. Rational explanation of experimental momentum profiles provides solid evidence that the trans conformer is slightly more stable than the gauche conformer, in accordance with thermodynamic predictions and other experiments. The case of ethanol demonstrates the significance of considering vibrational effects when performing a conformational study on flexible molecules using electron momentum spectroscopy.

Imaging molecular geometry with electron momentum spectroscopy

Electron momentum spectroscopy is a unique tool for imaging orbital-specific electron density of molecule in momentum space. However, the molecular geometry information is usually veiled due to the single-centered character of momentum space wavefunction of molecular orbital (MO). Here we demonstrate the retrieval of interatomic distances from the multicenter interference effect revealed in the ratios of electron momentum profiles between two MOs with symmetric and anti-symmetric characters. A very sensitive dependence of the oscillation period on interatomic distance is observed, which is used to determine F-F distance in CF4 and O-O distance in CO2 with sub-Ångström precision. Thus, using one spectrometer, and in one measurement, the electron density distributions of MOs and the molecular geometry information can be obtained simultaneously. Our approach provides a new robust tool for imaging molecules with high precision and has potential to apply to ultrafast imaging of molecular dynamics if combined with ultrashort electron pulses in the future.

Note: A high-efficiency multi-coincidence method designed for molecular fragmentation studies

A high-efficiency multi-coincidence method is developed based on the hardware electronic multiple coincidence units. The multi-hit signals originating from one single detector can be selected and measured in coincidence. The performance of the method is tested by the electron impact three-body fragmentation of CO2(3+). Compared to the conventional method, the relative and absolute coincidence efficiencies of the triple-coincidence measurement are improved by about 200 and 3 times, respectively.

Development of an electron momentum spectrometer for time-resolved experiments employing nanosecond pulsed electron beam

The low count rate of (e, 2e) electron momentum spectroscopy (EMS) has long been a major limitation of its application to the investigation of molecular dynamics. Here we report a new EMS apparatus developed for time-resolved experiments in the nanosecond time scale, in which a double toroidal energy analyzer is utilized to improve the sensitivity of the spectrometer and a nanosecond pulsed electron gun with a repetition rate of 10 kHz is used to obtain an average beam current up to nA. Meanwhile, a picosecond ultraviolet laser with a repetition rate of 5 kHz is introduced to pump the sample target. The time zero is determined by photoionizing the target using a pump laser and monitoring the change of the electron beam current with time delay between the laser pulse and electron pulse, which is influenced by the plasma induced by the photoionization. The performance of the spectrometer is demonstrated by the EMS measurement on argon using a pulsed electron beam, illustrating the potential abilities of the apparatus for investigating the molecular dynamics in excited states when employing the pump-probe scheme.

Observing interference effect in binary (e, 2e) of molecules

We present investigations on the two-center and multi-center interference effects of molecules in binary (e, 2e) experiments. The high energy resolution electron momentum spectroscopy (EMS) measurements on H2 are reported with final vibrational states resolved. The experimental momentum profiles for ionization transitions to the individual final vibrational states of the ion are obtained. The measured and calculated vibrational ratios of the cross sections deviate from Franck-Condon principle, which can be ascribed to the Young-type two-center interference. Furthermore, with the help of our latest version of EMS spectrometer which has considerably higher sensitivity and much wider momentum range from 0 to 8 a.u., we are able to extend our observations to multi-center interference effect in high symmetry molecules like NF3 and CF4 with several oscillation periods included.

Multi-center interference effect on (e, 2e) electron momentum spectroscopy

The multi-center interference effect of three outermost molecular orbitals (MOs) of CF4 is investigated using (e, 2e) electron momentum spectroscopy. We show that the observed oscillations are directly informative of the nature of molecular structure. By fitting the experimental results, the bond length of F-F of gas phase CF4 is determined.

Non-sequential and sequential fragmentation dynamics of OCS3+ in collision with 500 eV electron

Non-sequential and sequential fragmentation dynamics of OCS3+ investigated by electron collision at impact energy of 500 eV is reported in this abstract. By using Dalitz plot together with momentum correlation spectrum various dissociative channels are distinguished.